Preparation of quinonediimines from phenylenediamines using hydrogen peroxide and a catalyst

Abstract

A phenylenediamine compound can be converted, with high selectivity, into its corresponding quinonediimine by reacting the phenylenediamine with hydrogen peroxide in the presence of a catalyst.

Having thus described the invention, it is claimed:  
     
       1. A process for preparing a quinonediimine by reacting a corresponding phenylenediamine with hydrogen peroxide in the presence of a catalyst. 
     
     
       2. The process of claim  1  wherein the catalyst is a solid catalyst selected from a palladium/carbon (Pd/C), platinum/carbon (Pt/C), iron oxide (FeO 2 ), copper (II) oxide (CuO 2 ), manganese oxide (MnO 2 ), silver (Ag), a water soluble ionic metal catalyst, activated carbon or a modified activated carbon catalyst said modified activated carbon catalyst characterized by having surface oxides removed therefrom. 
     
     
       3. The process of claim  1  wherein the phenylenediamine is an ortho- or para-phenylenediamine of the following Formula I:                    
       wherein R 1  and R 2  and R 3  are the same or different and are selected from hydrogen, hydroxyl, halogen, alkyl, alkoxy, aryl, aralkyl, alkaryl, cycloalkyl, heterocycle, acyl, aroyl, carbamyl, carboxylic acids, esters, ethers, ketones, alcohols, thiols, alkylthiols, and cyano, and further wherein the resulting corresponding quinonediimine is of the following Formula IIa or IIb:                    
       wherein R 1 , R 2  and R 3  and are the same as in the compound of Formula I. 
     
     
       4. The process of claim  3  wherein R 1 =1,3-dimethylbutyl, R 2 =phenyl, and R 3 =hydrogen. 
     
     
       5. The process of claim  4  wherein the compound of Formula I is N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine. 
     
     
       6. The process of claim  3  wherein the quinonediamine is a para-quinonediamine. 
     
     
       7. The process of claim  6  wherein R 1  and R 2 =1,4-dimethylpentyl, and R 3 =hydrogen. 
     
     
       8. The process of claim  6  wherein R 1 , and R 2  are selected from isopropyl, sec-butyl, cyclohexyl, phenyl, and hydrogen. 
     
     
       9. The process of claim  1  wherein the reaction takes place in the presence of a solvent system selected from a homogeneous or a two-phase solvent system. 
     
     
       10. The process of claim  9  wherein the solvent is a two phase solvent system comprising a water insoluble organic solvent in combination with water. 
     
     
       11. The process of claim  9  wherein the solvent system is a homogeneous solvent system comprising one or more water soluble organic solvents. 
     
     
       12. The process of claim  10  wherein the water insoluble organic solvent comprises hexanes. 
     
     
       13. The process of claim  11  wherein the water soluble solvents are selected from acetonitrile and dimethylformamide (DMF). 
     
     
       14. The process of claim  1  wherein the reaction takes place at a temperature of between 25° C. and 70° C. 
     
     
       15. The process of claim  1  wherein the hydrogen peroxide is present in an amount ranging from about 1.05 to about 2.05 parts per equivalent of phenylenediamine. 
     
     
       16. The process of claim  1  wherein the strength of the hydrogen peroxide is between 10% and 35%. 
     
     
       17. A process for preparing a quinonediimine by reacting the corresponding phenylenediamine with hydrogen peroxide in the presence of a catalyst wherein the phenylenediamine is an ortho- or para-phenylenediamine of the following Formula I:                    
       wherein R 1 , R 2  and R 3  are the same or different and are selected from hydrogen, hydroxyl, halogen, alkyl, alkoxy, aryl, aralkyl, alkaryl, cycloalkyl, heteroocycle, acyl, aroyl, carbamyl, carboxylic acids, esters, ethers, ketones, alcohols, thiols, alkylthiols, and cyano, and further wherein the resulting corresponding quinonediimine is of the following Formula IIa or IIb:                    
       wherein R 1 , R 2  and R 3  are the same as in the compound of Formula I, wherein the reaction takes place in a homogenous solvent system or in a two-phase solvent system comprising a water insoluble organic solvent and water. 
     
     
       18. The process of claim  17  wherein the homogeneous solvent is selected water soluble organic solvents. 
     
     
       19. The process of claim  18  wherein the water soluble organic solvent is selected from acetonitrile and dimethylformamide (DMF). 
     
     
       20. The process of claim  17  wherein the water insoluble organic solvent of the two phase solvent system comprises hexanes. 
     
     
       21. The process of claim  17  wherein the catalyst is a solid catalyst selected from a palladium/carbon (Pd/C), platinum/carbon (Pt/C), iron oxide (FeO 2 ), copper (II) oxide (CuO 2 ), manganese oxide (MnO 2 ), silver (Ag), a water soluble ionic metal catalyst, activated carbon or a modified activated carbon catalyst said modified activated carbon catalyst characterized by having surface oxides removed therefrom. 
     
     
       22. The process of claim  17  wherein the compound of Formula I is N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine.